Objectives: It was known that workers in synthetic leather company are mainly co-exposed to dimethylformamide(DMF) with methyl ethyl ketone(MEK) or toluene(TOL) instead of a single dimethylformamide. This study was examined to the physico-chemical properties in single DMF and binary mixture DMF with MEK or TOL. Materials: Physico-chemical properties were measured by Korean and American Standard Test Methods. Results: Boiling point, specific gravity and flash point in single DMF were significantly higher than binary mixture DMF with MEK or TOL and such difference was dependent on the mixing ratio of MEK and TOL, and low explosion limit in binary mixture DMF with TOL was only significantly lower than single DMF. However, Reid vapor pressure had significantly higher in binary mixture DMF with MEK or TOL compared with single DMF. Conclusions: Our results demonstrate that the binary mixture DMF with MEK or TOL synergistically increases volatilization of DMF. It was concluded that the interaction between DMF and MEK and/or TOL might play a key role in the volatilization process of DMF under environmental conditions of workplace.